Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/465—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an acryloyl group, a quaternised or non-quaternised aminoalkyl carbonyl group or a (—N)n—CO—A—O—X or (—N)n—CO—A—Hal group, wherein A is an alkylene or alkylidene group, X is hydrogen or an acyl radical of an organic or inorganic acid, Hal is a halogen atom, and n is 0 or 1
  • C09B62/47—Azo dyes

Definitions

• This invention provides valuable new water-soluble azo dyestuffs which contain at least one aromatically bound a,B-dichloroor dibromopropionylamino group. More especially it provides o-sulfobenzene-o'-hydroxy or -o'-aminomonoazo naphthalene dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound azfl-dichloroor dibromopropionylamino groups, which dyestuffs may be further substituted in the benzene radical by lower alkyl, lower alkoxy, phenoxy, acetylamino, chlorine or bromine.
• benzenemonoazosulfonaphthalene dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound azfi-dichloro or dibromo propionylamino groups, which dyestuffs may be further substituted in the benzene radical by amino, lower alkyl or lower alkoxy.
• the invention also provides o-sulfobenzene or sulfonaphthalenemonoazo pyrazolone dyestuffs containing at least two and at most three sulfonic acid groups and at I least one and at most two aromatically bound azfi-dichloroor -dibromopropionylamino groups, which dyestuffs may be further substituted in the diazo component by lower alkyl, lower alkoxy, phenoxy, acylamino other than a,/3-dihalo-genpropionylamino, chlorine or bromine and in which dyestuffs the coupling component is a 3-methyl or 3-carboxy-5-pyrazolone bound to the azo-linkage in 4-position.
• Included in the invention are moreover complex chromium, cobalt or copper compounds of monozao dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound a2fi-dichloroor -dibromopropionylamino groups, which dyestufi's correspond to the formula wherein R is the radical of an o-hydroxybenzene or an o-hydroxynaphthalene which may be further substituted by lower alkyl, lower alkoxy, acylamino other than a,B-dihalogeno-propionylamino, chlorine or bromine and R, is the radical of a hydroxyor aminonaphthalene bound to the azolinkage in o-position to a hydroxy or amino group or the radical of a 3-methylor 3-carboxy-5-pyrazolone bound to the azo-linkage in 4- position.
• the instant invention also relates to disazodyestuffs containing at least two and at most four sulfonic acid groups and at least one and at most two aromati-cally bound azB-dichloroor dibromopropionylamino groups, which dyestuffs correspond to the formula II(') IIIH,
• R is an o-sulfobenzene radical which may be further substituted by lower aklyl, lower alkoxy, tn'fluoromethyl, chlorine or bromine, one X is hydrogen and the other X is a sulfonic acid group and R is a benzene radical which may be substituted by lower alkyl, trifluoromethyl, chlorine or bromine, sulfo or nitro.
• the term lower means: containing up to 4 carbon atoms.
• Valuable are e.g. diazo components in which the radical D, has the formula slogH S
• Dyestuffs of the general formula H0 8 SOal'I OaH SlOaH for the radical of a diazo component e.g.
• K stands for the radical of a hydroxynaphthalenesulfonic acid which may be further substituted, e.g.
• D stands for the radical of a diazo component which contains at least one sulfonic acid group and may contain an azo group, e.g.,
• IIOaS-C N N or IIOKS- NH-A and K for the radical of a coupling compound which couples in the adjacent position to an enolizable keto group, e.g.
• the dyestufi itself contains at least two sulfonic acid groups.
• Metal complex compounds of monoazo dyestuffs having at least two acid-solubilizing groups and at least one a,B-dichloroor dibromopropionylamino group.
• Suitable metal atoms are chromium, cobalt, nickel, and copper atoms, the last-named being preferred.
• suitable coupling compounds are l-(amino)aryl-5-pyrazolones and aminohydroxynaphthalenesulfonic acids.
• the a,B-dichloroor dibromo propionyl radical may be attached to the coupling compound, for instance in the following combination:
• a,,8-dichloroor dibromopropionyl radical may be attached to both the diazo-component and the coupling-component, e.g. in the following combination wherein A and R possess the aforecited meanings.
• Naturally 2:1 metal complexes as well as 1:1 complexes can be produced.
• the former contain preferably chromium or cobalt metal atoms.
• the dyestuffs of this invention may be obtained from dyestuff components which already contain the dihalogenated propionyl radical.
• Such dyestuff components are obtainable by methods in themselves known, for example, by the acylation of appropriate compounds with a halide or anhydride of an 64 :B-dihalogen-propionic acid.
• Suitable compounds for this purpose are those which contain an easily acylatable amino group, for example, a monoalkylamino group or a primary amino group, and in the case of diazo-components, a less easily acylatably primary amino group, and in the case of coupling components either a less easily acylatable amino group or a hydroxyl group responsible for coupling.
• amino groups that are less readily acylated there may be mentioned principally those which occupy a position vicinal to an acid group, for example, a sulfonic acid group. Aminohydroxy-compounds are acylated in such manner that esterification of the hydroxyl group is avoided.
• soluble organic dyestuffs which can be made in the above manner, there may be used metal-free or metalliferous monoazo-and disazo-dyestuffs which latter may also be prepared by metallisation. Esepcially good results are obtained with soluble azodyestufi's which possess no affinity for cotton or at most no pronounced affinity therefor.
• amino-azo-dyestuffs may be obtained, e.g., by hydrolysis of acylamino-azodyestuffs, by reduction of the nitro groups of nitro-azodyestuffs or by coupling a diazotized aromatic amine with a coupling component containing an acylatable amino group.
• disulfonic acid 2-ureido-5-hydroxynaphthalene-7-sulfonic acid, 2-carbethoxyarnino-5-hydroxynaphthalene-7- sulfonic acid, Z-B-methoxycarbethoxyamino-S- hydroxynaphthalene-7-sulfonic acid, l-(n-butyrylamino)-8-hydroxynaphthalene-3,6(or
• dyestuffs containing acylatable amino groups for use in the process of this invention, to be acylated, for example, with a dichloro or dibromopropionic acid halide or a corresponding acid anhydride, there may be mentioned the following (the acylatable amino group is italicized; the shade obtained with the acylated dyestuff is indicated in parenthesis):
• acylation of such a dyestuff containing an acylatable amino group with one of the aforesaid dihalogenpropionic acid halides or anhydrides is advantageously carried out in the presence of an acidbinding agent such as sodium acetate, sodium hydroxide or sodium hydrogen carbonate and under relatively mild conditions, for example, in an organic solvent or at a relatively low temperature in an aqueous medium.
• an acidbinding agent such as sodium acetate, sodium hydroxide or sodium hydrogen carbonate
• the dyestuffs of this invention are new. They are suitable for dyeing or printing especially polyhydroxylated materials of fibrous structure such as cellulosic materials, and also synthetic fibers, for example, of regenerated cellulose, or natural materials, for example, cellulose, linen or above all cotton.
• aqueous alkaline solutions which may contain a high content of salts
• the dyestuff is fixed on the material to be dyed by a heat treatment, for example, by steaming, in the presence of an alkali, or preferably by storing the dyed or printed material at room-temperature or at a slightly elevated temperature, e.g., at a temperature between 15 and 40C for 1 to 24 hours according to the socalled cold-pad-batch-process.
• Due to the reactive dihalogenopropionylamino substituent a chemical bonding is formed between the chromophore of the azo dyestuff and the cellulosic fiber during the fixation process.
• the dyeings are thoroughly rinsed with cold and hot water.
• they may also be treated with a dilute and advantageously slightly alkaline boiling solution of a nonionic detergent or a dispersing agent for a short time, for example, 5-10 minutes.
• Dyeings produced on cellulosic fibers with the dyestuffs of this invention are usually distinguished by the purity of their tints, by their good fastness to light and above all by their excellent fastness to washing.
• azB-dibromopropionyl chloride instead of 4.8.
• wfi-dichloropropionyl chloride a product is obtained which likewise dyes cotton fast greenish yellow tints.
• Example 2 8.76 parts of the dyestufi' of the formula OH SOaH SOQH are neutralized with sodium carbonate in 300 parts of water, and 6.56 parts of anhydrous sodium acetate are added. While stirring vigorously, a solution of 3.8 parts of azfi-dichloro propionyl chloride in 5 parts of toluene is added dropwise at -5C within 10 minutes. After a short time the acylation of the amino group is complete. The dyestuff is salted out with 70 parts of sodium chloride, filtered off and dried in vacuo at 60 to 70C. The dyestuff obtained in this manner dyes cotton bluish red tints.
• H03S- N N Hols NH2 SOsH 4 W W i if 7 1 m Scarlet.
• N- N N nois NH-Q s 03H '0 o n carbonate, and the dyestuff is salted out with sodium chloride and filtered off.
• the dyestuff dyes cotton reddish grey tints.
• the parent dyestuff of the above formula is obtain- Example 6 able, for example, by coupling diazotized 5-nitro-2- aminophenol with hydroxynaphthalene-3:6-disulfonic acid and reducing the nitro group in the resulting dyestuff to an amino group by means of sodium hydrosulfide.
• Z-phenylamino-S- 5 31.4 parts of 4-(a:fi-dichloropropionylamino)-laminobenzene-2-sulfonic acid are dissolved in 600 parts of water with the addition of sodium carbonate. 30 parts of hydrochloric acid of 30 percent strength are added at 0 to 5C, and the mixture is diazotized with 25 parts by volume of 4Nsodium nitrite solution. The diazo suspension, which gives an acid reaction to Congo, is then added to an ice-cold solution of 42.3 parts of l-benzoylamino-8-hydroxy-naphthalene-3:6- disulfonic acid and 30 parts of sodium carbonate in 400 parts of water. On completion of the coupling the dyestuff is salted out with sodium chloride, filtered off and dried in vacuo at 60 to C.
• the coupling can be carried out with advantage in the presence of sodium acetate or sodium bicarbonate.
• 5-(mB-dichloropropionylamino)- l-aminobenzene-Z-sulfonic acid can be prepared from 5 -amino-1-aminobenzene-2-sulfonic acid.

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• 1957
  • 1957-05-07 CH CH4578957A patent/CH384747A/de unknown
• 1958
  • 1958-04-28 DE DEC16733A patent/DE1212655B/de active Pending
  • 1958-05-06 GB GB14521/58A patent/GB885815A/en not_active Expired
  • 1958-05-06 ES ES0241745A patent/ES241745A1/es not_active Expired
• 1969
  • 1969-11-12 US US00876069A patent/US3755290A/en not_active Expired - Lifetime

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